DE1909107C3 - Mono- and disazo dyes which are free from acidic, water-solubilizing groups, processes for their production and their use for dyeing or printing fibers made from aromatic polyesters - Google Patents

Description

The present invention relates to new acidic water-solubilizing groups, in particular azo dyes which are free of sulfonic acid and carboxyl groups and which have at least one above one of its Carbon atoms bonded directly to a carbon atom of the remainder of a heterocyclic diazo component Pyridine ring included. The dyes according to the invention correspond to the general formula

D-N = N-

(CH ₂ ) "- Z '- (CH ₂ )"

wherein X, Y and Y _{1 are} hydrogen, trifluoromethyl, alkanesulfonyl, alkyl, alkoxy, aryloxy, arylthio, halogen or acylamino, R ₁ , R ₂ and R _{3 are} hydrogen, alkyl or substituted alkyl, «1, 2 or 3 and Z ' Pontic of the formula

X '(B Y') ^ ri- (R ') ^ Ti (Y' B) ^ r ₁ -X '

denotes where B denotes a —CO—, —SO ₂ - or lower alkylene bridge, X 'and Y' denotes an oxygen or sulfur atom or a nitrogen, in particular an —NH bridge, or a direct bond, where the two X 'or Y 'and B can be different from one another, R' is a C ₂ - Q-alkylene, a phenylene radical which is optionally substituted by methyl or a thiophene radical and p, q and r are I or 2, but ρ + q + r is at least 4 is mean.

2. Process for the preparation of azo dyes of the formula (1)

where η I or 2

D is a 1,2,4-thiadiazole or 1,3,4-thiadiazole radical and

A the remainder of a coupling component from one of the jo classes

a)

or

C ₂ H ₅

C ₂ H ₄ N (C ₂ H ₅ ),

NHCOCH,

or

-N O

in which D and A and η have the meanings given in Claim 1, characterized in that η mol of a diazo compound of an amine of the formula

D-NH,

wherein R ₁ and R ₂ independently of one another are H, C ₁ -C ₄ -alkyl, methoxy, ethoxy, benzyl, chlorine or CF _{1, NH-CO-CH 3} , NH-CO-CH ₅ , NH-CHO, NH-CO -OC ₂ H ₅ , and R ₃ and R ₄ independently of one another H, hydroxyethyl, methoxyethyl, / f-cyanoethyl, / (- chloroethyl, / i-acetoxyethyl, butyl, ethyl, methyl, phenyl, benzyl, / i-cyanoethoxyethyl, /) '-C, -C ₃ -alkylcarbonyloxyethyl or / i-dimethylaminoethyl or

OH

b)

Oll

(Hler

where D has the meaning given, with a Coupling component A free of sulfonic acid and carboxyl groups kuppel !.

wherein R = H, CH ₃ or OCH ₃ or

N (R ₅ ),

c) // \ S

wonn

R ₅ = H, CH ₃ , C ₂ H ₅ , phenyl,

R ₆ = SO ₂ -NH (CH ₂ J ₃ -N (CH ₃ ), or H, or

d) indoles of the formula

wherein

R ₇ = H, CH ₃ phenyl R ₈ = H, CH ₃

R ₉ = H or CH ₃

R ₁₀ = ethoxy, Cl, NO ,, CN, F, Br R ₁₁ = Cl, CH ₃

R ₁₂ = methoxy, Cl

R ₁₃ = CH ₃ , cyanoethyl or H or

e) pyrazoles of the formula

wherein

R ₁₃ = cyanoethyl,

h) one of the bifunctional radicals of a coupling component

SO ₂ -NH-C ₂ H ₄ -N (C ₂ Hs) ₂

/ ^ - Hydroxyaryl, Phenyl, Chlorphenyi. H. CH ₃ , C ₄ H ₉ ,

R ₁₄ = H, CH ₃ , COOCH ₃ R ₁₅ = OH, NH ₂
is or

f) quinolines of the formula OH

OH

or

g) barbaric acid. Miwie 1.3 lndandion. l.K-naphthindandione or dimedon. further

'- (CH ₂ ) .- UC >

R, '

N- (CH ₂ J ₁₁ -Z'- (CH ₂ J _n -N

wherein X, Y and Y _{1 are} hydrogen, trifluoromelhyl, alkanesulfonyl, alkyl, alkoxy, aryloxy, arylthio, halogen or acylamino, R ₁ , R ₂ and R _{3 are} hydrogen, alkyl or substituted alkyl, π 1, 2 or 3 and Z ' Pontic of the formula

Xi ι rj \ /> \ / η f \ / \ r ' rj \ x /' | DI in - \ V ^ Jq - 1 V * * ^ 'r - 1 ^

denotes where B is a CO, SO ₂ or, membered alkylene bridge, X 'and Y' denotes an oxygen or sulfur atom or a nitrogen, in particular an —NH bridge, or a direct bond, the two X 'or Y 'and B can be different from one another, R' is a C ₂ —Q-alkylene, a phenylene radical optionally substituted by methyl or a thiophene radical and p, q and r are 1 or 2, but ρ + q + r is at least 4, mean. The dyes according to the invention are prepared by methods known per se by adding η mol of a diazo compound of an amine of the formula

I - (- D-NH,

where D has the meaning given, with a coupling component free of sulfonic acid and carboxyl groups A couples.

As examples of diazo compounds used in the preparation by coupling are above all Aminothiazoles, aminothiadiazoles and aminotriazoles, for example the following:

5-Amino-3- (.? 'V- or 4'-pyiiuyl) -1.2.4-thiadia / ol.

2 - / \ mino-5- (2-, 3'- or 4'-py;: nyl) -l.3.4-thiiidiazul.

3-Ληιιηο-5- (2-. V- ο, ι, μ-.-1'-r> vriHvli-1 .2.4-triayol.

Numerous coupling components can be used as the coupling component, for example those the benzene or naphtha series or from the series of heterocyclic coupling components, such as them specified above s; na. From the clutch "> components of the benzene series are, in addition to the phenols, like μ-Krcsol, especially the aminobenzenes gun.nint, for example

Aniline, 3-methylaniline, ι ο

2-methoxy-5-methylaiHline,

^ Acciyl-amino-1-aminobenzene, N-methylaniline,

and in particular those of the formula

CH, CH, OCH, CH, CN

CH ₂ CH, OCH, CH, CN

NHCOR4

N / i-Methoxyäthylaniüii,
C.

yy

N - ^ - cyanoethylaniline,
N - ^ - chloroethylaniline,
Dimethylaniline,
Diethylaniline,
N-methyl-N-benzylaniline,
Nn-butyl-N-zf-chloroethylaniline, N-methyl-N- ^ i-cyanoethylaniline, N-methyl-N-fi-hydroxyethylaniline, N-ethyl-N- ^ - chloroethylaniline, N-methyl-N-zi-acetoxyethylaniline . N-ethyl-N - ^ - methoxyethylaniline. N - ^ - cyanoethyl-N-zi-chloroethylaniline. N-ethyl-N-tf-methoxyethylaniline, N- ^ i-cyanoethyl-N-zi-chloroethylaniline, N-cyanoethyl-N-acetoxyethylaniline, NN-di- ^ - hydroxyethylaniline, NN-di-zi-acetoxyethylaniline,
N-Ethyl-N ^ -liydroxy-S-chloropropylaniline, N ^ -Di - ^ - cyanoethylaniline,
KN-Di - ^ - cyanäthyl-S-methylaniline, N-fi'-Cyanathyl-N-zT-hydroxyathyl-S-chloraniline,

N.N-Di-ji-cyanoethyl-S-methoxyaniline, N ^ -Dimethyl-S-acetylamino-aniline, N-Ethyl-N - ^ - cyanoethyl-S-acetylaminoaniiin, N ^ J-Di-zi-cyanathyl-z-methoxy-S-acelylaminoaniiin,

N-methyl-N-phenacylaniline,
N - ^ - Cyanä thy l-2-chlorani] in,
N, N-diethy] -3-trifluoromethylaniline, N-ethyl-N-phenylaniline,
Diphenylamine.
N-methyldipehylamine,
N-methyl-4-ethoxydiphenylamine or N-phenylmoφholin.

further z. B. Amines of the formula

R, '

R ₃ 'where R ₁ and R ^ have the meaning given. Coupling components of the formula

CH ₂ CH ₂ -O-CH ₂ CH ₂ CN

20th

CH ₂ CH ₂ - O - CO - alkyl

and

25th

30th

- CH ₂ CH ₂ -O-CH ₂ CH ₂ CN

obtained in which R 'has the meaning given and X _{2 is} an acylaminogmppe, and in which alkyl is, for example, a methyl, ethyl or propyl group.

The following coupling components are listed as such examples:

40

45 OCH ₃

ζ ~ \ - N- (CH ₂ CH ₂ OCH ₂ CH ₂ CN) ₂ NHCOCH ₃

OC ₂ H ₅

N (CH ₂ CH ₂ OCH ₂ CH ₂ CN) ₂ NHCHO

NHCORi

where R ₁ 'denotes a hydrogen atom, an alkyl or alkoxy group, R ₂ "denotes a cyanoalkoxy group, RJ denotes a hydrogen atom, a cyanoalkoxyalkyl group or an acyloxyalkyl group and Ri denotes a hydrogen atom, an optionally substituted alkyl, cycloalkyl or alkoxy group or a benzene radical,

55

60

65

₃ CH ₂ CH ₂ OCH ₂ CH ₂ CN

\
.CH ₂ CH ₂ OCOCH ₃

NHCOCH ₃

<^ \ - NHCH ₂ CH ₂ OCH ₂ CH ₂ CN NHCOCH ₃

NHCH ₂ CH ₂ OCH ₇ Ch ₂ CN V-NHCH ₂ CH ₂ OCH ₂ CH ₂ CN NHCh ₂ CH ₂ OCH ₂ CH ₂ CN S-carbomethoxy-pyrazolone-S, Quinolines, like that

1 -Methyl- ^ hydroxyquinolone-1,

^r ) quinoline

or pyrimidines, such as

Barbituric acid, as well

1,3-indanedione,

1,8 napthindadione or ι «called Dimedon.

Other suitable coupling components are those which have a quaternizable or wear quaternized group, such as B. N-methyl-N, 2 - dimethylaminoethylaniline, N, 2 - (N '- ethyl N'-phenyl) aminoethylpyridinium chloride. further e.g. Connections of the formulas

QH ₅

NHCOOC ₂ H ₅ OCH ₃

NHCOCH ₃

C ₂ H ₄ N (C ₂ Hs) ₂

C ₂ H ₄ CN

CH ₃

NHCH ₂ CH ₂ OCH ₂ CH ₂ Cn

NHCOCH ₂ CH ₃

From the series of coupling components of the naphthalene series, apart from the naphthols, for example 1- or 2-naphthylamine and 2-pheny 1-aminonaphthalene, l-dimethylaminonaphthalene or called the 2-ethylaminonaphthalene. Out of line of the heterocyclic coupling components are, for example, the indoles, such as

2-methylindole,

2,5-dimethylindole,

2,4-dimethyl-7-methoxyindole, 2-phenyl- or 2-methyl-5-ethoxyindole, 2-methyl-5- or -6-chloroindole, 1,2-dimethylindole,

1-methyl-2-phenylindole, 2-methyl-5-nitroindole, 2-methyl-5-cyanoindole, 2-methyl-7-chloroindole, 2-methyl-5-fluoro- or -5-bromoindole, 2-methyl-5,7-dichloroindole or 2-phenylindole,

l-cyanoethyl-2,6-dimethylindole, also pyrazolones, such as. B. that l-phenyl-5-amino-pyrazole or 3-methyl-pyrazolone-5 or that 1-phenyl-S-methyl-pyrazolone-S, 1, S-dimethyl-pyrazolone-S, 1 -Butyl-S-methyl-pyrazolone-S, l-oxyethyl-3-methyl-pyrazolon-5, 1 -Cyanäthyl-S-methyl-pyrazolon-S, 1 - (o-chlorophenyl) -3-methylpyrazolon-5,

H ₂ CC-CH ₃

so Furthermore, diazotizable amines, such as. B. l-amino-3-methylbenzene, 1 - amino - 2 - methoxy - 5 - methylbenzene, 1-aminonaphthalene, etc. can be used so that Aminoazo dyes are formed, which in turn diazotizes and combined with the coupling components mentioned above to form disazo or polyazo dyes can be.

Finally, binary coupling components come into question, such. B. those of Formulas

Ri

R ₃

Ri

11th

(CH ₂ ) ^ - N

(CH ₂ ), - Z '- (CHA-N

where X, Y and Y _{1 are} hydrogen, trifluoromethyl, alkane

sulfonyl, alkyl, alkoxy, aryloxy, arylthio, halogen or acylamino, R ₁ , R ₂ and R _{3 are} hydrogen, alkyl or substituted alkyl, «1, 2 or 3 and Z 'is a bridge member of the formula

-X'— (B-Y '), - = i— (RVi- (Y'-BVzr-X' -

denotes where B is a CO, SO ₂ or lower alkylene bridge, X 'and Y' denotes an oxygen or sulfur atom or a nitrogen, in particular a - NH bridge, or a direct bond, where the two X 'or Y 'and B can be different from one another, R' is a substituted or unsubstituted heterocyclic, aromatic or optionally aliphatic radical interrupted by heteroatoms, and p, q and r are 1 or 2, but p + q + r must be at least 4. Such coupling components on which a diazotized amine can be coupled on each side are, for. B. named:

CH ₁ CH ₁ CN NC-CH ₁ -CH ₁

I "" I

N-CH ₁ -CH ₁ -O-Cu-O-CH ₁ CH ₂ -N

(CH ₁ CO-O-CH ₂ CHj) ₂ N

NHCO-C C -C-CONH

N- (CH ₂ CH ₁ -U-COCH ₃ ),

NC-CH ₁ CH ₁ -NH

NHCH ₁ CH ₁ CN

H, C, - N

NHCOCh ₁ CH ₁ COHN

NC ₂ H ₅

(CH ₂ ) -, Λυ Au (CH ₂ ), O CO (CHife— CO

NC ₂ H ₅ H ₅ C ₂ N

(CH ₂ ), (CH ₂ ),

Ο — COCO — O

H ₅ C ₂ -N- (CHi) ₂ -O (CH ₂ ) -NC ₂ H ₅

-NH ₅ C ₂ -N-

CH ₃ ⁽ ^ ^{Η2> 2 (} ^ " ² ' ² CH ₃

O CO O

Ο - CO - NH - + CHiV- NH-CO-O

! I ₅ C ₂ -N - <

ν M f IJ

(CH ₂ ),

Ο —CO —NH

NH-CO-O

H ₅ C ₂ -N - <^^ J> <^> - N — C ₂ H, (CH,), (CH,),

I "I"

Ο -COHCH ₂ ^ ₃ -CO-O

Instead of a single diazo component, it is also possible to use a mixture of two or more of the components according to the invention Diazo components and instead of a single coupling component a mixture use two or more of the coupling components according to the invention.

The diazotization of the diazo components mentioned can be carried out by methods known per se, e.g. with the help of mineral acid, especially hydrochloric acid, and sodium nitrite or z. B. with a solution of Nitrosylsulfuric acid in concentrated sulfuric acid, take place.

The coupling can also be carried out in a manner known per se, for. B. in neutral to acidic agents, if appropriate in the presence of sodium acetate or the like, influencing the coupling speed Buffer substances or catalysts, such as. B. pyridine, respectively. its salts, are made.

The dyes obtained according to the invention are suitable for dyeing and printing the most diverse fully synthetic fibers, such as B. of polyvinyl chloride, polyamide, polyurethane fibers, also of Fibers made from polyesters of aromatic dicarboxylic acids, such as. B. of polyethylene terephthalate fibers, in particular but from polyacrylonitrile fibers or from polyvinylidenecyanide fibers (Darvan). Under polyacrylonitrile fibers one understands above all polymers, which more than 80% z. B. 80 to 95% acrylonitrile; Besides do they contain 5 to 20% vinyl acetate, vinyl pyridine, vinyl chloride, vinylidene chloride, acrylic acid, Acrylic acid ester, methacrylic acid, methacrylic acid ester, etc.

On these fibers, which can also be dyed in a mixture with one another, one obtains with the new dyes intensive and level dyeings with good lightfastness and good all-round fastness properties, especially good washing, sweat, sublimation, wrinkle-proof, decatur, ironing, rubbing, carbonizing, Fastness to water, seawater, dry cleaning, paint and solvents. The invention new dyes have, inter alia. also good stability in a larger pH range, good affinity z. B. in aqueous solutions of different pH values and good Beuchfastness. Also show The new dyes generally have a good reserve on wool and other natural polyamide fibers.

The specified dyes are particularly suitable for trichromatic coloring. Furthermore, they are due to their hydrolysis resistance advantageously suitable for high temperature dyeing and for that Dyeing in the presence of wool. They can also be applied to the fibers by printing will. For this purpose, a printing paste is used, for example, which contains the dye together with the Contains aids commonly used in printing. They are also suitable for bulk coloring of Polymerization products of acrylonitrile, as well as of other plastic, possibly dissolved masses, in light and washfast nuances, also for the coloring of oil paints or varnishes, or finally also for the dyeing of cotton, especially of stained cotton, of cellulose, regenerated Cellulose and paper.

The new, according to the invention, non-water-soluble dyes which have a pyridine radical have a tertiary nitrogen atom, are expediently in finely divided form and with addition of dispersants such as soap, sulphite cellulose liquor or synthetic detergents, or a combination various wetting and dispersing agents are used. As a rule, it is useful to use these dyes before dyeing in a dye preparation containing a dispersant and finely divided Contains dye in such a form that when the dye preparations are diluted with water a fine dispersion Such dye preparations can be produced in a known manner, for. B. by falling over of the dye from sulfuric acid and grinding the slurry thus obtained with sulphite waste liquor, if necessary also by grinding the dye into highly effective

Milling devices in dry or wet form with or without the addition of dispersing agents Grinding process is preserved. They are also for Suitable for dyeing and printing a wide variety of semi-synthetic and fully synthetic fibers, such as z. B. of cellulose acetate, polyolefin, ζ. Β. modified polypropylene, polyacrylonitrile, polyvinyl chloride. Polyamide or polyurethane fibers, but especially fibers made from polyesters of aromatic dicarboxylic acids, such as B. of polyethylene terephthalate fibers.

To achieve strong colors, e.g. Example, on polyethylene terephthalate fibers, it has proven advantageous to add to the dye bath a swelling agent, or else to carry out the dyeing under pressure at temperatures above 100 ⁰ C, for example at 12O ⁰ C,. Suitable swelling agents are aromatic carboxylic acids such as benzoic acid or salicylic acid, phenols such as o- or p-oxydiphenyl, aromatic halogen compounds such as chlorobenzene, o-dichlorobenzene or trichlorobenzene. Phenylmethylcarbinol or diphenyl. When dyeing under pressure, it is advantageous to make the dyebath slightly acidic, for example by adding a weak acid, e.g. B. acetic acid.

The new dyes prove to be particularly suitable for dyeing using the so-called thermosetting process, after which the fabric to be dyed with an aqueous dispersion of the dye, which expediently contains 1 to 50% urea and a thickener, in particular sodium alginate, is preferably impregnated at temperatures of at most 60 ° C and squeezed off as usual. Appropriate one squeezes off in such a way that the impregnated goods contain 50 to 100% of their initial weight in dyeing liquid holding back.

To fix the dye, the fabric so impregnated, expediently after previous drying, for. B. in a warm air stream to temperatures of over 100 ⁰ C, for example between 180 to 220 ⁰ C, heated.

The heat setting process just mentioned is of particular interest for dyeing blended fabrics made of polyester fibers and cellulose fibers, especially cotton. In this case the Padding liquid in addition to the dye to be used according to the invention for dyeing cotton suitable dyes, for example direct dyes or vat dyes, or in particular so-called Reactive dyes, d. H. Dyes that form a chemical on the cellulose fiber Bond can be fixed, for example dyes containing a chlorotriazine or chlordiazine radical. In the latter case it proves to be expedient to add an acid-binding agent to the padding solution, for example an alkali carbonate or alkali phosphate. Alkali borate or perborate or mixtures thereof admit it. When using vat dyes, the padded fabric must be treated heat treatment with an aqueous alkaline solution of a reducing agent commonly used in vat dyeing necessary.

The according to the specified V '^ their on polyester fibers The dyeings obtained are subjected to an aftertreatment, for example by heating with an aqueous solution of an ion-free detergent.

The present dyes are also useful

/ lim V - '. i rhi "» n von Μκι'ΗιΊ'ΐν ^ Ιιι'η ιιις Pol vnclprf ^ c ^ rn and wool, whereby the wool portion remains reserved and can be dyed with a wool dye afterwards.
Instead of by impregnation, the present dyes can also be applied by printing in accordance with the specified processes. For this purpose one uses z. B. a printing ink that is finely dispersed in addition to the auxiliaries customary in printing, such as wetting agents and thickeners

κι dye optionally mixed with a dei above-mentioned cotton dyes, optionally in the presence of urea and / or an acid-binding agent Contains means.

According to the specified procedure, strong dyeings and prints of excellent quality are obtained Fastness properties, especially good light, sublimation. Fastness to decatur, washing and chlorinated water. A Another advantage of the new dyes is their good wool and cotton reserves, as well as that Drying stability and the low tendency to boil in the presence of wool.

Compared to the disperse dyes of BE-PS 6 40 973 are particularly the improved sublimation fastness on polyester materials, a larger one

; ■ "> Color strength on Ctilulose-272-acetate and an improved To highlight dye build-up on cellulose triacetate.

In the following examples, unless otherwise stated, the parts are by weight

κι parts, the percentages percentages by weight, and the temperatures are given in degrees Celsius.

example 1

To a mixture of 85 parts by volume of 1 n-Nitroü sylsulfuric acid and 90 parts by volume of a mixture of propionic acid and glacial acetic acid in a ratio of 1: 6 a solution of 14.25 parts of 5-amino-3 - (3'-pyridyl) -1, 2,4-thiadiazole in 90 parts is added at 0 ° to 5 ° of the above-mentioned propionic acid / glacial acetic acid mixture 4 <i and then stirred for 4 hours in an ice bath. After adding 3 parts of urea are stirred for a further hour and the diazo solution is then added to a solution of 12.8 parts of N-methyl-N, 2-cyanoethylaniline in 200 parts Glacial acetic acid flow. 800 parts of ice water are then added and the free mineral acid is blunted by addition of sodium acetate down to a pH of 4. After diluting with a further 800 parts of water it is heated to 50 ° and the practically completely precipitated dye of the formula is filtered off

-C-N

N C-N = N

CH ₁

CH, CH, CN

away. It dyes polyester fibers from aqueous dispersion in real scarlet tones.

If one uses instead of 5-amino-3- (3'-pyridyl) -

bo 1,2,4-thiadiazole 5-amino-3- (2'-pyridyl) -1, 2,4-thiadiazole or 5-amino-3- (4'-pyridyl) -l, 2,4-thiadiazole, dyes with similar properties are obtained.

Other dyes, the polyester fibers in the column III of the table below i) color shade is obtained. if you look at the information of the example proceeds instead of N-methyl-N.2-cyanoethylaniline but those in column II

909 635/49

1 2-methylindole

2 diphenylaniine

3 2-naphthylamine

4 dimethylaniline

5 N.N-biscyanoethyl-l ^ -toIuidine

6 Ν, Ν-biscyanoethylaniline

Example 2

substance of the formula

Ml

yellow

Red

Red

violet

Scarlet fever

Scarlet fever

10

15th

3.56 parts of 2-amino-5- (2'-pyridyl) -1, 3,4-thiadiazole are in 20 parts of a mixture of propionic acid and glacial acetic acid in a ratio of 1: 6 and the resulting solution to a mixture of 22 parts by volume 1 n-nitrosylsulfuric acid and 20 parts of the above-mentioned propionic acid / glacial acetic acid mixture 0 ° added dropwise with stirring. The mixture is stirred for 3 hours at 0 to 5 °, 2 parts of urea are added, then after a further A solution of 3.2 parts of N-methyl-N, 2-cyanoethylaniline for 30 minutes in 20 parts of glacial acetic acid. The solution obtained is introduced into 800 parts of ice water and the purple solution by adding 100 parts of crystallized sodium acetate to one pH 3 to 4 brought. The fancy coloring

CH, CH, CN

is suctioned off, washed with water and dried. It dyes polyester fibers from aqueous dispersion in real red tones.

Example 3

16.1 parts of 3-amino-5- (3'-pyridyl) -1,2,4-triazole are dissolved in 100 parts of 4N hydrochloric acid and at 0 ° by adding 25 parts by volume of a 4N solution of Sodium nitrite diazotized in water. In the diazo solution, a solution of 15 parts of N ₁ N-diethylaniline in 100 parts of 1-η hydrochloric acid and represents the coupling mixture by adding sodium acetate neutral to Congo red. The precipitated dye is filtered off with suction, washed with water and dried. It dyes polyester fibers in real orange tones.

Other dyes, the polyester fibers in the column IV of the table below Shades of color are obtained according to the information in Examples 1-3 by diazotizing the in column II specified diazo components and couplings on the coupling components listed in column III.

Ill

IV

C-N

N C-NH,

C ₂ H ₅

C ₂ H ₄ OH ruby

the same

violet

C ₄ II,

the same

the same

dcsL'l.

Red

ruby

violet

N (CMlO red

Cl- ".

continuation

C-N

Il Il

N C-NH, \ / S

8 the same.

the same

10 the same.

11 the same.

12 the same.

111

CH ₃

I.
CH,

CH,

CH,

? ^CHl CH ₄ OCOCH ₃

C ₂ H ₄ OC ₂ H ₄ CN NHCOOC ₂ H ₅

HC C-CH,

Il Il c ν

HO N

C ₂ H ₄ OH

C ₂ H ₅

C ₂ H ₄ OCOCH ₃

20th

violet

ru am

I λ the same.

14 the same

CH ₃

OCH.,

> - NHC ₂ H ₄ OC ₂ H ₄ CN NHCOCH ₂ CH.,

CO

violet

15 desul.

I. continuation i 0 23 Il 21 / ^ \ | 19 09 107 ill ML V_ LMj
Il Il C ^ ⁿ ' C ₂ H ₄ CN <'"" "/ - N' C ₂ H ₄ CN NIlCOCH., CH, 22nd IV j Cy L IN
Il Il Il Il
HO-C N
V /
N
I. <(^> - N (C ₂ H ₄ CN), yellow 16 i 17 Il Il
N C-NH,
\ /
S. C ₂ H ₅ I.
CH, CH, j <(^> - NH- ^ ~> - I 18 the same CH,
I. CMIaOCMl ₄ CN Scarlet fever 1 CH., - '; _N J _{X 7} < 19th 25th N
N / XCN
Il Il H Ί
OCH., Scarlet fever Ii Il
N C-NH,
\ /
S. C ₂ H, 20th the same violet C ₂ H ₄ CN the same orange 21 C ₂ H, NN
Il Il I _n J- Il Il
-C C-NH, ml the same violet the same ruby the same violet desul. Red

23

continuation

III

CIIj

C C-NH ₁

Ν —Ν

27 the same.

28 the same.

29 the same.

30 the same.

31 the same.

32 N.

33 desel.

34 the same.

35 the same.

C ₂ H ₄ CN
N (C ₂ H ₄ CN) ₂

NH

CH,

Ν — Ν

Il Il

C C-NH, \ / S

Λ-C-N

N C-NH, \ /

N H

CO

\ /
CO

CH ₂
HO

C = CH

N = C-CH ₃

C ₂ H ₅

si
No. ₂ H ₄ CN

NH ₂

24

CH ₂ -CH ₂
NO

CH ₂ -CH ₂

C ₂ H ₄ CN NC-C ₂ H ₄
NN

C ₂ H ₄ O-CO-OC ₂ H ₄

CH ₃

C ₂ H ₄ CN

IV

Red

Scarlet purple

yellow yellow

yellow

Red

violet

ruby

Red

yellow

25th

Continuation

26th

Il -c-
Il N
Il II C-CH ₃
H 37 <■ y Il
N
\
N-
H C-NH, < Y ⁷ N-NH, Il
N 38 the same ca- 39 the same T If " ¹ HL C.
/ \ / / \ /
HO N
H

40 the same.

41 the same.

42 the same.

43 the same

44 N.

45 the same

46 the same

NHCOCH ₃

C ₂ H

2 ⁿ 5

C-N

Il Il

N C-NH ₂ \ /

HC C-CH ₃

Il Il c ν

HO N

QH ₉ C ₂ H ₅

N \

C ₂ H ₁ OCO- (CH ₂ ) ₂ -

IV

Red

orange

greenish yellow

orange

yellow

orange

yellow

Red

yellow

yellow

Claims (1)

Patent claims: i. Mono- or disazo dyes, which are free of acidic water-solubilizing groups, thereby characterized in that they correspond to the general formula (1) D-N = N- (D J « d) indoles of the formula where η 1 or 2, D a 1,2,4-thiadiazole or 1,3,4-thiadiazole radical and A the radical of a coupling component from one of the classes R ₂ R ₄ C ₂ H ₅ QH ₁ N (C ₂ H ₅ J ₂ NHCOCH, wherein R ₇ = H, CH ₃ phenyl R ₈ = H, CH ₃ R ₉ = H or CH ₃ R ₁₀ = ethoxy, Cl, NO ₂ , CN, F, Br R ₁₁ = Cl, CH ₃ R ₁₂ = methoxy, Cl R ₁₃ = CH ₃ , cyanoethyl or H or e) pyrazoles of the formula V- / R ₁₅ - ^ N N // V -N wherein R ₁ and R ₂ independently of one another are H, C ₁ -Q-alkyl, methoxy, ethoxy, benzyl, chlorine or CF ₃ , NH-CO-CH ₃ , NH-CO-C ₂ H ₅ 4 »NH-CHO, NH -CO-OC ₂ H ₅ , and R ₃ and R ₄ independently of one another H, hydroxyethyl, methoxyethyl, / (- cyanoethyl, / i-chloroethyl, / i-acetoxyethyl, butyl, ethyl, methyl, phenyl, benzyl, / ί- Cyanethoxyethyl, / y-Ci-C ₃ -alkylcarbonyloxyethyl or 4> / i'-dimethylaminoethyl or OH or wherein R = H, CH ₃ or OCH ₃ or N (R ₅ J ₂ c) R, = H, CII ,. C ₂ IU. Phenyl. R _n = SO, NII (C 11, I ₁ N (CHJ ₂ or 11 is or wherein R _u = cyanoethyl, y λ SO ₂ -NH-C ₂ H ₄ -N (C ₂ H ₅ I ₂ / i-hydroxyethyl, phenyl, chlorophenyl, H, CH ₃ , C ₄ H ₉ , R ₁₄ = H, CH ₃ , COOCH ₃ R ₁₅ = OH, NH ₂ or O quinolines of the formula OH OH g) Barbiluric acid. as well as 1,3-indanedione, 1,8-naphthindanedione or dimedon. iernei h) one of the bifunctional radicals of the coupling components Z '- (CH ₂ J _n - R, D-N = N- N '' (D 3. Use of azo dyes according to claim 1 for dyeing and printing fibers of aromatic polyesters, in particular of polyethylene terephthalate.